Chemiluminescent reaction of substituted 2,2,3,3-tetrachloro-1,4-benzodioxane

ABSTRACT

NOVEL SUBSTITUED BENZODIOXANE COMPOUNDS WHICH PROVIDE CHEMILUMINESCENT LIGHT WHEN REACTED WITH OTHER NECESSARY CHEMILUMINESCENT REACTANTS IN THE DIRECT GENERATION OF LIGHT FROM CHEMICAL ENERGY. BY &#34;LIGHT&#34; AS REFERRED TO HEREIN IS MEANT ELECTROMAGNETIC RADIATION AT WAVELENGTHS FALLING BETWEEN ABOUT 350 MU AND ABOUT 1,000 MU.

United States Patent 3,749,677 CHEMILUMINESCENT REACTION OF SUBSTITU-TED 2,2,3,3-TETRACHLORO-1,4-BENZODIOXANE Donald Roy Maulding, BranchburgTownship, Somerset County, N.J., assignor to American Cyanamicl Company,Stamford, Conn. No Drawing. Filed Jan. 27, 1971, Ser. No. 110,294 Int.Cl. C09k 3/00 US. Cl. 252-188.3 CL 5 Claims ABSTRACT OF THE DISCLOSURENovel substituted benzodioxane compounds which provide chemiluminescentlight when reacted with other necessary chemiluminescent reactants inthe direct generation of light from chemical energy. By light" asreferred to herein is meant electromagnetic radiation at wavelengthsfailing between about 350 my and about 1,000 mu.

The invention herein described was made in the course of or under acontract with the Department of the Navy.

The present invention relates to novel benzodioxane compounds whichobtain chemiluminescent light when reacted With other necessarychemiluminescent reactants in the direct generation of light fromchemical energy. By light as referred to herein is meant electromagneticradiation at wavelengths falling between about 350 my and about 1000 mg.

The art of generating light from chemical energy, i.e.chemiluminescence, is continually in search of compositions which whenreacted substantially improve the intensity and lifetime of lightemission contrasted to known chemiluminescent compositions andreactions. Obviously, improved compositions are constantly in demand foruse as signal devices, for area illumination, etc.

Various compounds have been known and proposed in the past for obtainingchemiluminescent light. One group is based on the compoundtetrarnethylamino ethylene, reactive with oxygen. Such compounds mustobviously be protected from air during storage.

Another group of compounds are derivatives of his aryl or heterocyclicderivatives of oxalic acid. These compounds react with a peroxide in thepresence of a solvent and a fluorescent compound to givechemiluminescent light. Although these oxalates are the best knownchemiluminescent systems, they have the disadvantage that the oxalatesare relatively expensive to prepare and are also relatively insoluble,thus limiting the amount of light obtainable from a given volume ofsolution.

It is an object of this invention to obtain a chemiluminescentcomposition and a process employing said composition whereby a highefliciency may be obtained in the conversion of chemical energy intolight.

Another object is to obtain a chemiluminescent compound which produceslight over an extended period of time.

Another object of this invention is to obtain a chemiluminescentcomposition which attains light of substantially higher intensity andwith greater degree of quantum efliciency than has been obtained withformer chemiluminescent compositions.

Another object of this invention is to obtain a chemiluminescentcomposition which may be employed to obtain light by a process which ismechanically simple and which is economically inexpensive.

Another object of this invention is to obtain a chemiluminescentreactant which is stable over a long period of time and which may besubsequently reacted to obtain chemiluminescent light.

Another object of this invention is to obtain a chemi- 3,749,677Patented July 31, 1973 ICC luminescent reactant which when reacted willobtain chemiluminescent light by a process which is not hazardous.

Another object is to obtain a composition characterized by acontrollable (1) length of duration of chemiluminescence and (2)intensity of chemiluminescent illumination.

Another object is to obtain a process of regulating intensity andduration of chemiluminescence.

Other objects of this invention become apparent from the above andfollowing disclosure.

The term aryl group as used herein means a group which is derived froman aromatic compound by the removal of one or more atoms.

The term chemiluminescent reactant, as used herein, means (1) a mixturewhich will result in a chemiluminescent reaction when reacted with othernecessary reactants in the processes as disclosed herein, or (2) achemiluminescent composition.

The term fluorescent compound," as used herein, means a compound whichfl'uoresces in a chemiluminescent reaction, or a compound which producesa fluorescent compound in a chemiluminescent reaction.

The term chemiluminescent composition, as used herein, means a mixturewhich will result in chemiluminescence.

The term admixing, as used herein, means reacting or sufiicientlybringing together component reactants to obtain a chemiluminescentreaction.

The term hydroperoxide compound as used herein is limited to peroxidecompounds having at least one group, or a compound which upon reactionproduces a compound with such a group.

The term peroxidic groups," as used herein, represents HHO, R'OO--, or

o R'boo- R is defined for the polycarbonyl compound below, while R is asubstituent such as alkyl, cycloalkyl, m-hydroxyalkyl, substitutedalkyl, for example.

The term "diluent," as used herein, means a solvent or a vehicle whichwhen employed with a solvent does not cause insolubility.

The term peroxide compound, as used herein, also includes compoundswhich upon reaction produce the peroxide group.

The term hydrogen peroxide compound" includes (1) hydrogen peroxide and(2) hydrogen peroxide-producing compounds.

I have now found a new class of compounds which react with a peroxide inthe presence of a solvent and a fluorescent compound to givechemiluminescent light.

These compounds are novel benzodioxane derivatives having the generalstructural formula:

n Cl 0 01 wherein R represents an electronegative group such as, halo,i.e. bromo, chloro, and fiuoro; alkyl, aryl, NO CN, -CF

and R'O C, where R is alkyl or aryl, and hydrogen, provided at least oneof the R substituents is always an electronegative group.

Light emission is obtained by the reaction of the substitutedbenzodioxane with hydrogen peroxide in the presence of a fluorescer. Thelight intensity is increased substantially with increased substitutionof, e.g., with chloro groups. Ethyl benzoate can be used as solvent witht-butyl alcohol or B-methyl 3 pentanol as cosolvents. A two phase system(9 parts/one part by volume) of ethyl benzoate with 30% hydrogenperoxide provides an intensely bright system. With such flouorescers as9,10 diphenylanthracene, perylene, 9,10 bis (phenylethynyl)anthraceneand 5,12 bis (phenylethynyl) naphthacene, blue to red emission isproduced.

The hydroproxide employed in the compositions and process of thisinvention may be obtained from any suitable per oxide compound. Forexample, the hydroperoxide may be employed as sodium peroxide.Alternatively, sodium perborate may be placed in aqueous solutionwhereby a solution of hydrogen peroxide is obtained. Obviously, hydrogenperoxide or its solution may be employed. The peroxide employed may beobtained from anhydrous hydrogen peroxide compounds such as perhydrateof urea (ureas peroxide), perhydrate of pyrophosphate (sodiumpyrophosphate peroxide), perhydrate of histidine (histidine peroxide),sodium perborate, and the like. Still another form in which the H may beprovided in the composition is that of an anhydrous solution of H 0 in asuitable solvent such as an ether, an ester, an aromatic hydrocarbon,etc. of the type which would provide a suitable diluent for thecomposition of this invention. Alternatively, the hydroperoxide employedin the composition or process could be any compound having ahydroperoxidic group, such as hydroperoxide such as t-butylhydroperoxide and perbenzoic acid. Whenever hydrogen peroxide iscontemplated to be employed, any suitable compound may be substitutedwhich will produce hydrogen peroxide.

The hydroperoxide concentration may range from about 15 molar down toabout 10* preferably about 2 molar down to about molar. The genericcompound of this invention may be added as a solid or in admixture witha suitable solid peroxide reactant or in a suitable diluent, oralternatively dissolved directly in a solution containing the peroxidereactant.

Typical diluents within the purview of the instant discovery are thosethat do not readily react with a peroxide, such as hydrogen peroxide,and which do not readily react with the polycarbonyl compound or withthe rearranged polycarbonyl compound.

Although the addition of water tends to quench the production ofchemiluminescent light according to the present invention, water canserve as a partial diluent up to substantial major percentages (morethan 50%). The term water," as used herein, includes water-producingcompounds such as hydrates.

Any one or more suitable diluents may be included with or in the placeof the water, as long as the peroxide employed is at least partiallysoluble in one or more of the diluent(s), such as, for example, at leastone gram of H 0, per liter of diluent. The following are typicalillustrative examples of the diluents or solvents which may be singly orjointly employed: non-cyclic or cyclic others, such as diethyl ether,diamyl ether, diphenyl ether, anisole, tetrahydrofuran, dioxane, and thelike; esters such as ethyl acetate, propyl formate, amyl acetate,dimethyl phthalate, dicthyl phthalate, methyl benzoate, and

or a peroxy acid the like; aromatic hydrocarbons, such as benzene,xylene, toluene, and the like, acids such as acetic or propionic acids.

The fluorescent compounds contemplated herein are numerous; and they maybe defined broadly as those which do not readily react on contact withthe peroxide employed in this invention, such as hydrogen peroxide;likewise, they do not readily react on contact with the generic compoundof this invention. Typical suitable fluorescent compounds for use in thepresent invention are those which have a spectral emission fallingbetween 330 millimicrons and 800 millimicrons and which are at leastpartially soluble in any of the above diluents, if such diluent isemployed. Among these are the conjugated polycyclic aromatic compoundshaving at least 3 fused rings; such as: anthracene, substitutedanthracene, benzanthracene, phenanthracene, substituted phenanthracene,naphthacene, substituted naphthacene, pentacene, substituted pentacene,and the like. Typical substituents for all of these are phenyl, loweralkyl, chlorine, bromine, cyano, alkoxy (C -C and other likesubstituents which do not interfere with the light-generating reactioncontemplated herein.

Numerous other fluorescent compounds having the properties givenhereinabove are well known in the art. Many of these are fully describedin Fluorescence and Phosphorescence," by Peter Pringsheim, IntersciencePublishers, Inc. New York, 1949. Other fluorescers are described in TheColour Index," 2nd ed., vol. 2, The American Association of TextileChemists and Colorists, 1956, pp. 2907-2923. While only typicalfluorescent compounds are listed hereinabove, the person skilled in theart is fully aware of the fact that this invention is not so restrictedand that numerous otherfluorescent compounds having similar propertiesare contemplated for use herein.

It has been found that the molar (moles per liter of diluent)concentrations of the major components of the novel composition hereindescribed may vary considerably. It is only necessary that components bein sufiicient concentration to obtain chemiluminescence. The molarconcentration of Benzodioxane normally is in the range of at least about10* molar, preferably in the range of at least about 10- to about 5molar; the fluorescent compound is present in the range from about 1O toabout 5, preferably about 10' to about l0 molar; and the diluent must bepresent in a suflicient amount to form at least a partial solution ofthe reactants involved in the chemiluminescent reaction. There is noknown maximum limit on the concentration of the generic compound of thisinvention which may be employed in the reaction, and as discussed above,intense chemiluminescent light may be obtained by employment of the highconcentrations.

The ingredients of the composition of this invention may be admixed in asingle stage of admixing or in a sequence of steps of admixingingredients together or separately. Accordingly, alternativecompositions may be prepared which may be stored over a period of timeand which may be admixed with the final ingredient at a time when thechemiluminescent lighting is desired. For example, one such compositionwould be a composition which includes a generic compound of thisinvention and a fluorescent compound but which does not include aperoxide compound. Another alternative solid composition would be acomposition which includes a peroxide, but which does not include thefluorescent compound. Another alternative composition would be a solidcomposition which includes a solid generic compound of this inventionand a solid hydroperoxide compound, and which possibly additionallyincludes a solid fluorescent com pound, but which does not include adiluent. Obviously, the preferred compositions which would be less thanall necessary components to produce a chemiluminescent light would be acomposition which would be substantially stable to a practical degreeover an extended period of time; otherwise, there would be no realadvantage in forming a chemiluminescent reactant to be employed in asubsequent chemiluminescent reaction.

The wavelength of the light emitted by chemiluminescence of thecompositions of this invention, i.e., the color of the light emitted,may be varied by the addition of any one or more energy transfer agents(fluorescers) such as the known fluorescent compounds discussed atlength above.

The wavelength of the light emitted by the composition of this inventionwill vary, depending upon the particular fluorescent component employedin the reaction.

Although in the process of obtaining chemiluminescent light according tothis invention, it is normally not neces sary to employ a specific orderto sequence of steps in the adding of the individual ingredients of theinventive chemiluminescent composition, it has been found that thefluorescent component preferably should be already in the reactionmixture at the time of addition of the last component necessary to bringabout the chemical reaction and the concurrent release of chemicalenergy.

Additionally, it has been found that the superior intensity ofchemiluminescence is obtained when the final mixture producing theluminescence is maintained at a temperature of between about -40 C. and100 (3., preferably between about 20 C. and 50 C., the luminescense ofapplicants process is not limited to these ranges and temperature is notcritical.

The lifetime and the intensity of the chemiluminescent light can beregulated by the use of certain regulators such as (1) By the additionof Weak bases to the chemiluminescent composition to increase intensity.Both the strength and the concentration of the base are critical forpurposes of exactness in regulation.

(2) By the variation of hydroperoxide. Both the type and theconcentration of hydroperoxide are critical for the purposes ofexactness in regulation.

The following examples are intended to illustrate the present inventionand are in no way intended to limit the invention except as limited inthe appended claims.

EXAMPLE 1 Preparation of 5,6,7,8-tetrachloro-1,4-benzodioxane To asolution of 10.6 g. of tetrachloropyrocatechol monohydrate, 78 g. ofdibromoethane and 50 ml. of ethylene glycol which had been heated to 130was added portionwise 11.6 g. of anhydrous potassium carbonate duringtwo hours. The mixture was heated at 130 for another hour, cooled andpoured into water. Extraction with 50% benzene-ethyl ether gave a solidwhich was washed with methanol and recrystallized from chloroform. Theyield of light pink solid, M.P. 163-165 [lit.

M.P. 165] was 1.60 g. or 17%.

EXAMPLE 2 Chlorination of 5,6,7,8-tetrachloro-1,4-dioxane A refluxingsolution of 1.55 g. of 5,6,7,8-tetrachloro- 1,4-dioxane and 200 ml. ofcarbon tetrachloride was treated with chlorine gas while beingirradiated with a Hanovia 100 watt lamp (Pyrex filter) until a lightyellow color remained. Evaporation of solvent gave 2.20 g. (95%) ofcolorless solid, M.P. 128130.

Analysis-Calcd. for C CI O (percent): C, 23.30; Cl, 68.93. Found(percent): C, 23.02; C], 68.78.

In another experiment incomplete chlorination of a. solution of 1.64 g.of 5,6,7,8-tetrachloro-1,4-benzodioxane and 200 ml. of carbontetrachloride gave a colorless solid,

1 L. Hornet and H. Mel-z, Ann, 570, 89 (1950).

which was chromatographed on alumina and benzene to yield 1.01 g. (46%)of 2,3,5,6,7,8-hexachloro-1,4-benz0- dioxane, M.P. 189-192"; NMR, asinglet peak at 6.376.

AnaIysis.-Calcd. for C H Cl O- (percent): C, 27.98; H, 0.58; Cl, 62.09.Found (percent): C, 27.92; H, 0.67; Cl, 62.41.

EXAMPLES 3-5 In this example, perchloro-l,4-benzodioxane(5,6,7,8-chloro-1,4-dioxane) was examined for chemiluminescent activity. Theresults are shown in Table I.

TABLE I Chemiluminescence Results in Experiments withPerchloro-1,-t-benzodloxane (PCBD) H20: IEIXJD it LI. TIIL, 8 Test PCBout M Na0Ae,M lbts. em mm 1 0. 10 0. 0. 66 0. 48 l0 1 0. 10 0. 27 0. 660. d3 10 3 0.01 0.066 0.006 0.28 l0 4. 0. 10 0. 60 0. 28 4 5 0. 01 0.066 0. 29 4 Ex erirnents were run at 25 C. Solvent for PCBD and SUD-bis-(phony ethynyljanthracene was ethyl bcnzoate. Solvent for hydrogenperoxide was 3-methyl-3-pontano1 when base was not used. In experimentswith sodium acetate, acetic acid was used as solvent.

h Maximum intensity.

' Lifetime.

I claim:

1. A chemiluminescent composition intended to be reacted with ahydroperoxide to produce chemiluminescent light said compositioncomprising the ingredients, a compound of the formula or R o, 4

R 01 Cl and R"O C-, where R" is alkyl or aryl.

3. The composition of claim 1 wherein said peroxide is hydrogenperoxide.

4. The composition of claim 1 wherein said fluorescent compound is9,10-bis(phenylethynyl)anthracene.

5. The composition of claim 1 wherein said compound is a chlorinatedbenzodioxane.

References Cited UNITED STATES PATENTS 2,420,286 5/1947 Lacey 252-1883JOHN D. WELSH, Primary Examiner US. Cl. X.R.

